Sulfonated phenylamino-halotriazine or- diazine surface modified aminated hydrophobic fibers and blends thereof with unmodified aminated hydrophobic fibers

ABSTRACT

Hydrophobic fibers containing amino groups and having a dyereserved surface so as to render the fibers non-dyeable or differential-dyeable, and a process for their preparation.

' United States Patent [191 Moriyama et a1.

[451 Dec. 16, 1975 1 1 SULFONATED PHENYLAMINO-HALOTRIAZINE OR- DIAZINE SURFACE MODIFIED AMINATED HYDROPHOBIC FIBERS AND BLENDS THEREOF WITH UNMODIFIED AMINATED HYDROPHOBIC FIBERS [75] Inventors: Kazuo Moriyama; Takashi Iwato;

Morihiko Ohno, all of Takatsuki,

Japan [73] Assignee: Toyo Boseki Kabushiki Kaisha, Osaka, J apan [22] Filed: Oct. 10, 1972 21 Appl. No.2 296,207

[30] Foreign Application Priority Data v Oct. 8, 1971 Japan 46-79786 [52] US. Cl. 8/1155; 8/15; 8/65; 8/D1G. 21; 8/168; 28/7212; 28/74 R; 8/115 Primary ExaminerDonald Levy Attorney, Agent, or Firm-Wenderoth, Lind & Ponack 1 1 ABS! RACT Hydrophobic fibers containing amino groups and having a dye-reserved surface so as to render the fibers non-dyeable or differential-dyeable, and a process for their preparation.

9 Claims, 2 Drawing Figures US. Patent Dec. 16, 1975 SULIFONATED PHENYLAMINO-HALOTRIAZINE OR- DIAZINE SURFACE MODIFIED AIVHNATED HYDROPHOBIC FIBERS AND BLENDS THEREOF WITH UNMODIFIED AMINATED HYDROPHOBIC FIBERS The present invention relates to hydrophobic fibers containing amino groups of which only the surface layer is processed so as to be dye-reserving to render the fibers non-dyeable or differential-dyeable and also to a process for producing the same.

An object of the present invention is to provide hydrophobic fibers containing amino groups, which are non-dyeable or differential-dyeable with anionic dyes.

Another object of the present invention is to provide hydrophobic fibers containing amino groups which are ferential-dyeable with the use of only anionic dyes.

A further object of the present invention is to provide a process for producing the above-mentioned hydrophobic fibers containing amino groups which are nondyeable or differential-dyeable.

The invention will be explained in detail as follows by referring partly to the accompanying drawings wherein FIG. 1 is a schematic cross-section of a fiber embodying this invention and FIG. 2 is a schematic longitudinal sectional view of an apparatus useful for producing the fibers of this invention.

Referring to FIG. 1 which is a schematic cross-section of a single fiber of the present invention, the numeral 1 indicates a layer which has been processed to be dye-reserving to make the fiber non-dyeable or differential-dyeable (hereinafter referred to as dye-reserving layer, for simplicity) and the numeral 2 designates an ordinary dye-acceptable core portion of the fiber.

The hydrophobic fiber of the present invention preferably has a dye-reserving layer of a thickness of less than 2 microns on the average. As the thickness of the surface dye-reserving layer exceeds 2 microns on the average, the effect of the present invention is gradually decreased.

The existence of such dye-reserving layer 1 can be confirmed from the fact that, when the fibers of the present invention are dyed with an anionic dye, especially with a dye having more than three sulfonic acid groups, e.g. Drimarene Brilliant Red X-2B (a reactive dye produced by Sandoz) and are observed under a microscope, the fibers are dyed only from the cut ends.

The dye-reserving layer 1 is non-dyeable with anionic dyes because the amino groups in that layer of the hydrophobic fiber are blocked by covalent bonds. However, in reality, while some dyes cannot substantially pass through the dye-reserving layer, another can pass through that layer with comparative ease, unlike in the case of hydrophobic fibers which have completely been rendered non-dyeable or low dyeable to the core of the fibers. Thus, among anionic dyes, those having a single sulfonic acid group can pass through the dyereserving layer 1 to dye even the core of the fibers sutficiently. However, with the increase in the number of sulfonic acid groups in the dye it becomes more and more difficult for the dye to pass through the dyereserving layer and therefore the fibers do not become dyed. By the use of this phenomenon, the fibers of this invention can be dyed to have a multicolored effect. Of course it is possible to use another type of dye in combination, for example disperse dyes. Moreover, dyeing with anionic dyes gives dyed articles of bright color and having good fastness to wet treatment and light.

Hal H Z Ya NVN It is also possible to obtain more complex multi-colored effects when the dye-reserving layer is formed partly along the length of the hydrophobic fibers. The dyeability can be also varied in various ways by changing, for example, the thickness of the dye-reserving layer, the density of blocking; of amino groups, etc. Also, very attractive miulticolored effects can be obtained by the combination of dyes having different numbers of sulfonic acid groups.

The fibers of the present invention are suitable for producing yarn or cloth of a pepper-and-salt effect by the combination with other hydrophobic fibers containing amino groups having different dyeability or with fibers of other types. Especially the use of the fibers of the present invention in articles of interior decoration, such as carpets, gives multicolored products of charming effects that have not been obtained in conventional articles.

Generally, the hydrophobic fibers of the present invention can be produced by reacting a compound having groups capable of linking to amino groups in the fibers to form covalent bonds, with only the surface portion of the fiber. Such compounds having groups capable of forming covalent bonds with amino groups are preferably colorless or white compounds having reactive groups capable of reacting with amino groups, such as halotriazinyl, halopyrimidinyl, haloquinoxalyl, haloacrylamido, vinylsulfo groups, etc., or any other groups that can produce these groups. However, colored compounds may be also used for the purposes of the present invention. Also suitable are compounds having anionic groups, for example, sulfonate, carboxylate, sulfate, phosphate groups, ect., besides the highly reactive groups capable of reacting with amino groups.

More specific examples of such compounds are those having the following general formula:

Hal

N Z Y I Hal Hal N f commr- (A) n Hal \N 7 wherein Hal is F, C] or Br, Z is XY-(A),,, B is H, Cl or F, X is O, S or' -NR, Yis an (n+1)- valent substituted or non-substituted an aromatic or aliphatic group, A is anionic group, n is O or a positive integer, M is H, alkali metal or ammonium, and R is H or a lower alkyl group.

The hydrophobic fibers containing amino groups I Hal include polyamide fibers, such as nylon-6, nylon-66;

protein-acrylonitrile graft copolymer fibers such as Chinon (produced by Toyobo Co.): fibers of polyesters, polyurethanes, polyacrylonitrile, polypropylene, etc. which have been copolymerized, graft copolymerized or mixed with a compound having an amino group, for example, aminoalkyl acrylate, etc. Among them, polyamide fibers are most preferable.

The fiber to be treated with the above mentioned compound is usually in the form of fibers, filaments, yarn, but sometimes the treatment may be carried out in respect of the fibers in the form of woven fabrics, knitted fabrics, non-woven fabrics, or paper.

There are various methods for reacting the surface portion of the fiber with the compound having groups capable of linking to amino groups to form covalent bonds.

One of such methods is to apply the dye-reserving agent to the fibers in a mist-like state, in a manner as shown in FIG. 2, wherein the numeral 3 indicates a means for applying a dye-reserving agent to the fiber a. The reference numeral 4 indicates the main body of the treating apparatus, and the reference numeral 5 designates a supply pipe of high pressure gas. The filaments a to be treated are given the dye-reserving agent at low temperature on the surfaces by the dye-reserving agent applicator 3 and then fed into the treating apparatus 4 through supply rollers 6,6. Since the inlet 7 of the main apparatus 4 is narrowed and the high pressure gas supplied from the high pressure gas supply pipe 5 spurts out from the gas outlets 8,8 downwardly as a jet stream, the filaments a are drawn into the apparatus 4. The filament passage in the apparatus 4 is expanded sharply at the part 9, so that the jet stream turns into a violent turbulent stream therein. At this time, the filaments a are also violently vibrated to be opened, and the treating agent partly covering the surfaces of the filaments a leaves the filaments and floats in the form of mist to completely cover only the surface layer of the filaments again. The filaments having this surface deposit of the reserving agent are then dried by a heater 10 positioned at the lower part of the treating apparatus where the reaction on the filament surfaces is completed. The surface-treated filaments are taken-out by delivery rollers 11,11, and wound on a winding roller 12. If a compressed hot air is used as a high pressure gas, the heater 10 is not always necessary.

In the above mentioned method, the dye-reserving agent may be directly supplied at the inlet 7 of the treating apparatus or at the spreading part 9. If desired, the agent may be contained in the high pressure gas. The filaments are not necessarily required to be nontwisted yarn but may be soft-twisted yarn of less than 100 T/m.

Another example of treatment is that, an article to which the dye-reserving agent has been applied is squeezed and dried at low temperature and then subjected to heat treatment to fix the agent.

A further example of treatment is that unstretched filaments to which the dye-reserving agent has been applied is dried and then stretched to fix the agent by the heat developed by the stretching, or is stretched under heating to fix the agent.

In the above mentioned last two methods, it is preferable that the article-under treatment should not be brought to a temperature higher than 50C. before drying. If the article is raised above that temperature, the dye-reserving agent may penetrate into the core of the fibers and therefore the fibers of the present invention cannot be obtained. When the temperature is raised after drying, the dye-reserving agent reacts with the amino groups on the fiber surfaces and is fixed, so that it does not diffuse into the core of the fibers.

The dye-reserving agent may be used as an aqueous solution or an organic solvent solution. However, it is preferable to use it as an aqueous dispersion with suitable adjustment of the concentration and (wet) pick up such that the fibers take up 0.01 to 0.5% by weight of the agent based on the weight of the fibers.

When the dye-reserving agent is used in the form of an aqueous solution, the reactive groups in the agent may react with water and are hydrolyzed, so that the reactivity with amino groups is gradually lowered. Therefore, in such case it is preferable to lower the water solubility of the agent, for example by maintaining the treating liquor at a low temperature or by modifying the sulfonic acid groups into the form of their salts or free acid having slight water solubility or by adding a mineral salt such as sodium sulfate, sodium chloride, etc., so that the hydrolysis proceeds only from the surfaces of the dispersed particles and therefore the agent is kept stable.

The methods of forming a dye-reserving surface layer intermittently along the lengthwise direction of the fibers include (1) a method of applying the dye-reserving agent intermittently along the lengthwise direction of the fibers; (2) a method wherein after the agent is applied to the whole surfaces of the fibers and fixed at some parts of the surfaces, the dye-reserving agent on the other parts is removed; and (3) a method wherein after the dye-reserving agent is applied to the whole surfaces of the fibers and fixed, some parts of the surface layer are stripped off.

An example of the method (1) is that the travelling yarns are contacted intermittently with a dye-reserving agent-supplying roller. An example of the method (2) is that after the dye-reserving agent is applied and dried, some parts of the agent are fixed on the yarns or fabrics and the yarns or fabrics are then washed to remove the agent in the other parts. A peculiar example of this method is that after the dye-reserving agent is applied to unstretched filaments and dried, the filaments are stretched in some parts and the dye-reserving agent is fixed to the filaments by the heat developed by the stretching. In this case since the filaments are formed into thick-and-thin yarn, the contrasting difference of color is further emphasized to produce an interesting effect. Among examples of the method (3) is a method of pressing the fibers with a pair of gears, 21 method of scratching some parts of the fiber surfaces with an edge, a method of pressing some parts of the fibers with a hot roller, a method of passing the fibers through sands or glass powder, etc., a method of strongly pressing some parts of the fibers with engraved hot rollers, a method of strongly pressing the fibers superposed with rugged cloth as a lace or rugged paper, with hot rollers, etc.

The fibers thus obtained are dyed mainly with anionic dyes including ordinary acid dyes, metallized dyes, direct dyes, reactive dyes, etc., and any of such dyes can be used satisfactorily. As mentioned above, the dyeability of the fibers depends on the number of sulfonic acid groups contained in the dye. Examples of the dyes containing a single sulfonic acid group are C.l. Acid Yellow 25, 29, 49, 64, 65, 110, 135, 159, 168, G1. Acid Orange 116, 127, CI. Acid Red 32, 57, 257, 266. 333, 334, CI. Acid Violet 31, 41, Cl. Acid Blue 25, 27, 40, 41, 47, 62, 72, 78, 106, 129, 230, C1. Acid Green 83, C1. Acid Brown 248,etc. Examples of the dyes containing two sulfonic acid groups are C.l. Acid Yellow 17, 38, 42, 44, 79, CI. Acid Orange 33, CI. Acid Red 37, 154, 157, 168, CI. Acid Violet 48, Cl. Acid Blue 80, 112, 182, 203, CI. Acid Green 27, 4l, etc. Examples of the dyes containing three or more sulfonic acid groups are C.I. Acid Red 145, CI. Direct Red 95, Cl. Reactive Yellow 2, 12, CI. Reactive Orange 2, CI. Reactive Red 3, 4, 9, 12, 17, 56, CI.

EXAMPLE 1 Filament yarn of nylon-6 (1 100 d/68 f), while travelling, was brought into contact with the surface of a rotating roller dipped in a bath consisting of parts by weight disodium hydrogenphosphate water 2 parts by weight and 93 parts by weight.

so that the yarn could take up 3% by weight of the solution based on the weight of the fibers. The yarn was then introduced into a treating apparatus as shown in FIG. 2, while a jet stream of high temperature high pressure air at 190C. and 4 kg/cm was blown thereinto so that the yarn was opened into individual filaments and at the same time crimp-processed. At this time, the solution of the dye-reserving agent which covered the surfaces of the fibers more or less unevenly was blown off into fine mist-like droplets by the high speed jet stream, and the mist then covered the filaments again uniformly and became fixed by reacting with the amino groups on the surfaces of the fibers.

The yarn thus treated and yarn similarly crimp-processed but not treated with the dye-reserving agent were formed into twisted yarn. A carpet was prepared from this twisted yarn and was dyed in a bath containing C.l. Direct Red 95 1% o.w.f. and Ultra N-l (pH adjusting agent produced by Miteshima Chemical Co.) 0.2 g/liter at a liquor ratio of 1:50 and at a temperature of 100C. for 60 minutes. The result was that the yarn treated with the dye-reserving agent was not dyed at all while the yarn not treated was dyed in deep scarlet.

Undyed cut piecesof the both yarns (treated and untreated) were prepared and dyed with the abovementioned ddye. The cross-section of each of them was observed. Both were dyed in quite the same depth of color. It was observed under a microscope, however, that the surface layer of the yarn treated with the dye- 6 reserving agent was not dyed. The thickness of the dye-reserving layer of the treated yarn was about 1 micron when observed by means of microscopic photographs of the cross-sections of the fibers.

The content of amino groups as a whole was 55 milliequivalent/kg fibers for the untreated yarn and 53 milliequivalent/kg fibers for the yarn treated with the dye-reserving agent. Thus, there was no substantial difference between the two since the surface layer of which the amino groups were blocked was very thin.

EXAMPLE 2 Filament yarn of nylon-6 1 d/68 f), while travelling, was contacted intermittently with the surface of a rotating roller dipped in a bath consisting of 2 parts disodium hydrogenphosphate water 2 parts and 96 parts and immediately introduced into a treating apparatus as shown in FIG. 2 where it was treated as in Example 1. In this way. filament yarn was produced which had an intermittent thin dye-reserving layer (about 1 micron thick) formed evenly on the surface of the filaments.

The yarn was then formed into a carpet, which was dyed in a bath consisting of C.l. Acid Brown 248 1.2 7: o.w.f

Cl. Acid Red 57 0.2 7: o.w.f

C.1. Acid Blue 72 0.35 7; o.w.f

acetic acid 2 o.w.f. and water the balance at a liquor ratio of 1:50, at a temperature of 100C for 45 minutes.

The result was that the parts covered with the dyereserving agent were dyed medium brown while the parts not covered with the agent were dyed deep brown, thus producing a two tone effect. The state of the parts covered with the dye-reserving agent and the state of the parts not covered therewith were quite the same as in Example 1.

EXAMPLE 3 Threads of nylon filaments 1 100 d/68 f) arranged in parallel at intervals of 2 mm. were brought into contact with the surface of a roller rotated and dipped in a bath consisting of C C N H I II N N N I c] 2 parts sodium acetate 2 n and water 96 parts so that the threads could take up the solution. The threads'were then squeezed with a metallic roller to a pick-up of and dried gradually at 50C. Initially, only water was evaporated at such comparatively low temperature and a film of a liquid high in the concentration of the dye-reserving agent was formed on the surfaces of the fibers. When the temperature was elevated to 150C., the dye-reserving agent was reacted with the amino groups in the fibers and a dye-reserving layer was formed.

Thus treated filament yarn was twisted with filament yarn which had not been thus treated. The twisted yarn was dyed in an aqueous bath containing 1 0.2 g/liter C.l. Direct red 95 and Ultra N-l at a liquor ratio of 1:50 at a temperaure of lOOC. for 60 minutes.

The result was that, while the treated yarn was not dyed at all, the untreated yarn was dyed in a deep scarlet color.

The same twisted yarn was dyed in a bath containing C.l. Acid Yellow 17 0.5 o.w.f. Mylanthrene Brilliant Blue 3BLF (an acid dye produced by Althaus) l 7: o.w.f.

and acetic acid 0.5 7: o.w.f.

at a temperature of 100C. for 60 minutes. The result was that, while the untreated filament yarn was dyed green, the treated yarn was dyed blue. The cross-section of the treated filaments showed that the thickness of the dye-reserving layer was less than about 2 microns.

EXAMPLE 4 Five hundred threads of Exlan H type filaments (acid dye-dyeable acrylic fibers containing amino groups produced by Japan Exlan Company, Limited; 100 d/40 f) were arranged in parallel and were passed through a bath composed of C.l. Reactive Blue 10 and Ultra N-l at a liquorratio of 1:50 at a temperature of 100C. for 60 minutes. The result was that the treated yarn remained white while the untreated yarn was dyed in a deep navy blue to obtain a dyed checked fabric. The cross-section dyeing of the treated filaments showed that the thickness of the dye-reserving layer was less than 2 microns on the average.

EXAMPLE 5 Chips of nylon-6 having a relative viscosity of 2.5 were melted and spun into filament yarn at a temperature of 260C. and at a winding speed of 800 m/min. The filament yarn was made to take up the following treating liquor in an amount of 6 on the weight of the fibers from an oiling roller, and wound up.

spinning oil 5 sodium sulfate V the balance.

and water To prepare the bath, sodium sulfate was dissolved in water and the solution was cooled to 20C. The compound (a) was then added to the solution and dispersed by stirring with a high speed stirrer. This dispersion was mixed with the spinning oil which was then emulsified. The yarn was then stretched four times the initial length.

On the other hand, another sample of the same filament yarn was treated in the same way except that the oiling bath did not contain the compound (a), and was blended with the above-mentioned yarn which was treated with the compound (a). The resulting blended yarn was dyed with C]. Direct Red and yarn having a dotted effect of deep red and white was obtained. When dyed with C.I. Acid Yellow 135, the blended yarn was dyed in yellow colors with a slight difierence in depth, and when dyed with a mixture of CI. Direct Red 95 and Cl. Acid Yellow l35, the yarn represented an orange and yellow effect.

The above-mentioned bath was used continuously and the yarn spun after 5 days was examined for its shades after dyeing. It was found that the shades were substantially the same as those of the first day.

EXAMPLE 6 Filament yarn of nylon-6, while travelling, was

brought into contact with a roller rotated and dipped in a bath containing n NH N N and disodium hydrophosphate 0.5 71

Cl. Acid Red (containing two 35 sulfonic acid groups) 0.5 7: o.w.f. and Cl. Acid Blue (containing a single sulfonic acid group) 1.2 71 o.w.f.

at a liquor ratio of 1:50 and at a temperature of 100C. for 40 minutes. The modified yarn and the yarn of 40 ordinary dyeability were dyed blue and violet respectively. For the purpose of comparison, nylon-66 type 845 (Du Pont. deep dyeable) and type 846 (Du Pont, regular) were combined and dyed in the same way as mentioned above. However the multicolored effect was insufficient, being bluish violet and reddish violet.

EXAMPLE 7 Chips of nylon-6 having a relative viscosity of 2.5 were melted and spun into filament yarn at a spinning 5Q temperature of 260C. and a winding speed of 800 m/min. The yarn was made to take up a treating liquor composed of spinning oil 15 d water the balance in an amount of 6 on the weight of the fiber from an oiling roller and wound up. This unstretched yarn was stretched four times of the initial length. When the stretched yarn was dyed with Drimarene Brilliant Red X-2B, only the cut ends of the filaments were dyed. This yarn was combined with yarn treated in an oiling bath not containing the compound (b). When the combined yarn was dyed in a bath containing C.l. Reactive Blue 10 (containing 3 sulfonic acid groups) 1.0 7: o.w.f. and C1. Acid Yellow (containing a single sulfonic acid group) 0.3 7: o.w.f.

at a pH of 5.5 as in Example 1, the yarn was dyed yellow and deep blue.

EXAMPLE 8 Filament yarn of nylon-6 l 100 d/64 f), while travelling, was applied with a treating liquor l composed of $0 No Cl N I 3 N N V I disodium hydrogenphosphate -5 and water the balance and another treating liquor (2) composed of C N O3NO Y m- NH G N N disodium hydrogenphosphate and water the balance.

each independently and intermittently along the length of the yarn and thereafter crimp-processed by compressed hot air jet of C. and 4 kg/cm When the yarn thus obtained was dyed with Cl. Acid Blue 80 in the ordinary way, the parts not given the treating liquor (1) and (2) were dyed deep blue, the parts given the treating liquor (2) were dyed lightmedium blue, the parts given the treating liquor (l) were dyed light blue, and the overlapped parts of the treating liquor (1) and (2) remainded white.

When the yarn was dyed with C1. Acid Yellow 135, there was only a very slight difference in shade. When the yarn was dyed with a mixture of the two dyes, the above-mentioned parts were dyed blue green, green, yellow green and yellow, respectively, to produce a more complex effect.

When the yarn was dyed With the mixture of (Llv Acid Yeilcm 49 (cdll'lalliiilfl a single -continued The unstretched yarn. after being allowed to stand c.l. Acid Red 158 (containing 2 sulfonic for 2 days in a room at a temperature of 20C. and a 9" relative humiditv of 65 7:, was stretched by a drawand (,l. RCHCIIYC Blue 10 (containing 3 sulfonic acid groups) 03 5 twister. The stretching ratiowas intentionally varied intermittently to produce thick-and-thin yarn (stretchin ratio at thick arts, 1.8 times; thin arts, 4 times). h parts glven h treatmg hquqr l 1 the treatmg Ai ter being washe d with water, the yarn was dyed with hquor both.hquor and not gwen elther of them C.I. Acid Yellow 29 (containing a single sulfonic acid were dyed reqdlsh yellow Orange yellow and deep 10 group). Yarn having very contrasting colors was obbrown respectwely' tained, the thick parts being dyed deep and the thin EXAMPLE 9 p ght.

The following twokinds of treating liquor containing dye-reserving agents were applied to filament yarn of Deep dyeable nylon-66 yarn containing 72 milnylon-6 intermittently along the length of the yarn and liequivalent/kg. fiber of amino groups was subjected to were fiXed y the mfithOd 215 Show" in EXamPle surface dye-reserving treatment according to the method as shown in Example 1. This filament yarn was plyed with crimp-processed light dyeable nylon-66 having an amino group content of 37 m.eq./kg. fiber. Y N(CH3) Q The plyed yarn was dyed in an aqueous solution con- N v N EXAMPLE 1 l taining 1 of o.w.f. of CI. Acid Yellow 49 (containing a single sulfonic acid group) at 100C. for 45 minutes in I the usual way. The result was that the dye-reserving l 5 treated yarn was dyed deeper than the light-dyeable dmdmm hydrogenphosphae 05 yarn. However, when dyed with G1. Acid Blue 80 (conand water the balance taming two sulfonic acid groups) in the same was as above, the dye-reserving treated yarn was dyed lighter than the light-dyeable yarn. Also, when dyed with C1. Reactive Red 3 or Cl Reactive Blue 10 (both containmg three sulfonic acid groups) in the same way as W NH Q above, the dye-reserving treated yarn was not substanand tially dyed. When the plyed yarn was dyed with a combination of the above-mentioned dyes (each 0.5

o.w.f.), it was dyed in various colors as follows:

Dyereser\'ing Light dyeable (1 OH treated yarn yarn N c.l. Acid Yellow 49 fl N Cl. Acid Blue 80 greenish yellow bluish green I ll 40 ct Acid Yellow 49 N N N c Cl. Reactive Red 3 yellow scarlet V c N N Cl. Acid Yellow 49 I I C.Iv Reactive Red 3 c I c H 2 x -l- C.l. Reactive Blue 10 yellow deep brown nd u ter the bulanc e. what claimed 153 l. Hydrophobic fibers having a dye-reserving layer When the yarn was dyed with C.I. Acid Blue 80, it only on the surface of each individual fiber, produced was dyed deep blue, light blue, green and yellow. by a method which comprises subjecting hydrophobic A tufted carpet was produced from the above-menfibers containing amino groups to the action of a turbutiOnFd treated y f was y with Acid Blue lent gas stream to cause exposure of the individual 80 m One'bath i 1 carpet shqwed the filaments thereof, and simultaneously therewith deposeffect of colors and in addition much higher bulklness iting a dye reserving agent in mist form on the fibers,

than that produced from yam-dyed yarn.

and subsequently fixing the dye-reserving agent on the EXAMPLE 0 fibers by subjecting the resultant fibers to a dry heat Nylon-6 was meltn and th ar b f i di treatment, to form said dye-reserving layer, said dyewas made to take up 6 by weight of a liquor of the reserving agent being a compound selected from the following composition. group consisting of compound of the formulae:

c l N Hal N z V l" Y Y N N N 1 Hal 5 parts h d h h wherein Hal is fluorine, chlorine or bromine, Z is iso lum ro en es ate 4 spinning oil g p p 8' gig NR-phenyl sulfonate, B is hydrogen. chlorine or fluoand wutcr ilic hdldncc. rine and R is hdyrogen or lower alkyl.

2. The hydrophobic fibers as claimed in claim 1 wherein the thickness of the dye-reserving layer is less than about two microns.

3. The hydrophobic fibers as claimed in claim I wherein the dye-reserving layer is present intermittently along the lengthwise direction of the fibers.

4 Polyamide fibers according to claim 1.

5. Polyamide fibers according to claim 1, said fibers being mixed with polyamide fibers not having the dyereserved surface layer thereon 6. The hydrophobic fibers as claimed in claim 1 wherein the dye-reserving agent is applied to the fibers, and the resultant fibers are subjected to the action of wherein the dye-reserving agent is a dichlorotriazine.

UNITED STATES PATENT OFFICE QERTIFICATE OF CORRECTION Patent No. 3,926,548 Dated December 16, 1975 Inventor(s) Kazuo Moriyama, Takashi Iwato and Morihiko Ohno It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In claim 1, after the structural formula following line 12, insert (1 Hal N Z an \f Hal Signed and Scaled this Second Day Of May 1978 .s+iu.

RU'I'H (I .\I.-\S()\ LU'l'Rl-ILLE F. PARKER Arresting ()jlicvr Acting ('nmmissiom-r of Patvnnand Trademarks 

1. HYDROPHOBIC FIBERS HAVING A DYE-RESERVING LAYER ONLY ON THE SURFACE OF EACH INDIVIDUAL FIBER, PRODUCED BY A METHOD WHICH COMPRISES SUBJECTING HYDROPHOBIC FIBER CONTAINING AMINO GROUPS TO THE ACTION OF A TURBULENT GAS STREAM TO CAUSE EXPOSURE OF THE INDIVIDUAL FILAMENTS THEREOF, AND SIMULTANEOUSLY THEREWITH DEPOSITING A DYE-RESERVING AGENT IN MIST FORM ON THE FIBERS, AND SUBSEQUENTLY FIXING THE DYE-RESERVING
 2. The hydrophobic fibers as claimed in claim 1 wherein the thickness of the dye-reserving layer is less than about two microns.
 3. The hydrophobic fibers as claimed in claim 1 wherein the dye-reserving layer is present intermittently along the lengthwise direction of the fibers.
 4. Polyamide fibers according to claim
 1. 5. Polyamide fibers according to claim 1, said fibers being mixed with polyamide fibers not having the dye-reserved surface layer thereon.
 6. The hydrophobic fibers as claimed in claim 1 wherein the dye-reserving agent is applied to the fibers, and the resultant fibers are subjected to the action of the turbulent gas stream to form a mist of the dye-reserving agent which has been applied to the fibers, said mist then being deposited on the fibers.
 7. The hydrophobic fibers as claimed in claim 1 wherein the gas used to form the turbulent gas stream contains the dye-reserving agent, or the dye-reserving agent is blown directly into the turbulent gas stream, thus forming the mist of the dye-reserving agent.
 8. The hydrophobic fibers as claimed in claim 1 wherein the dye-reserving agent is a dihalotriazine.
 9. The hydrophobic fibers as claimed in claim 8 wherein the dye-reserving agent is a dichlorotriazine. 